辅助气体对RF-PECVD制备碳纳米管薄膜形貌的影响

采用射频等离子体增强化学气相沉积(RF-PECVD)技术,以Ni为催化剂,经600℃裂解C2H2在Si基底上制备出定向碳纳米管薄膜。采用扫描电子显微镜(SEM)表征了刻蚀后Ni颗粒与沉积的碳纳米管薄膜的形貌。研究了辅助气体对等离子体预处理催化剂与碳纳米管生长的影响。结果表明:辅助气体(H2与N2)流量比对催化剂颗粒尺寸、分布以及碳纳米管生长有显著影响;合适的气体流量比有利于减少碳纳米管薄膜的杂质颗粒,促进其定向生长。预处理过程中气体流量比H2:N2=20:5时,预处理后催化剂Ni颗粒分布密度大、粒径小且分布范围窄,适合碳纳米管均匀着床;沉积生长碳纳米管薄膜时,H2:N2=20:15可得到纯度高、定向性好的碳纳米管。     

定向碳纳米管薄膜的制备

以二茂铁为催化剂前驱体,氢气为载气,乙炔为碳源,硅片作衬底,用化学气相沉积法,采用不同的催化剂引入方式,在700℃下分别制备出定向碳纳米管薄膜及非定向碳纳米管薄膜.并基于实验结果对影响生长定向碳纳米管的因素进行分析,表明催化剂颗粒的诱导作用是导致生长定向碳纳米管的重要原因.     

用ECR-CVD方法制备定向碳纳米管

以FeaO4纳米粒子为催化剂,CH4和H2为气源,采用电子回旋共振微波等离子体化学气相沉积技术(ECR-CVD)在多孔硅基底上制备出定向生长的碳纳米管.研究了气氛组成、气压、温度和反应时间对碳纳米管生长特性的影响.使用扫描电子显微镜(SEM)、透射电子显微镜(TEM)和拉曼光谱(Raman spectrum)表征了样品的形貌和结构.结果表明:气氛组成和气压影响了反应腔内离解碳的浓度,从而影响碳纳米管的成核、生长速度及定向生长;温度的变化改变催化剂的尺寸从而改变碳纳米管的直径,在过低的温度下碳纳米管不能实现定向生长;碳纳米管随着反应时间的延长而不断增长,但超过一定时间后催化剂颗粒被碳包覆而失去催化作用,生长停止.     

包覆纳米镍粒子的碳纳米管磁性研究(英文)

通过溶胶 -凝胶超临界干燥技术制备出NiO SiO2 比为 1.2的二元气凝胶纳米催化剂 ,并以气凝胶为催化剂通过化学气相热解法合成了碳纳米管 ;碳纳米管的合成是在石英管式炉中完成。将催化剂置于石英舟中 ,在流动氮气中将管式炉加热至所需的温度 ,然后通入甲烷、氢气混合气体 ,热解反应 30min～ 6 0min后形成碳纳米管。反应结束后 ,生成的碳纳米管在氮气氛中冷却至室温。采用XRD、SEM、TEM、HRTEM、Raman分析手段对制得的碳纳米管进行了表征 ,并测定其磁化系数。结果表明 :裂解产物主要由碳纳米管和纳米镍粒子组成 ,且纳米镍粒子包覆于碳纳米管的顶端。这种包覆纳米镍粒子的碳纳米管的比饱和磁化强度和矫顽力分别为 0 .6 6A·m2 ·kg- 1 和2 0 15 7A·m- 1 。     

碳纳米纤维在纳米催化剂上的不同生长形态

利用纳米镍、酒石酸铜催化剂,通过碳的化学气相沉积法(CVD)分别制备出并列形态和"V"形态生长的碳纳米纤维,并通过透射电子显微镜(TEM)、扫描电子显微镜(SEM)对其进行了观察研究,发现生长在催化剂粒子上的碳纳米纤维在初始生长时的生长方向与催化剂粒子形状之间有密切关系.我们分析认为,在碳纳米纤维的生长过程中,碳在催化剂粒子中的扩散速度是控制步骤,并且决定催化剂粒子晶面上不同生长点的纤维生长速度.     

纳米碳纤维的低温制备——催化剂粒子尺寸的影响

以采用电阻加热法制备的纳米铜粒子为催化剂,在低温下催化乙炔制备了纳米碳纤维。所制备的纳米碳纤维具有螺旋型和直线型两种形貌。采用透射电子显微镜(TEM)和扫描电子显微镜(SEM)对纳米碳纤维进行了表征。纳米铜催化剂粒子在催化纤维的生长过程中,经历了一个重要的形状变化过程。催化剂粒子尺寸对所制备的纳米碳纤维的形貌有很大的影响。通常有两根螺旋纳米碳纤维以对称模式在单个粒径小于50nm的催化剂粒子上生长,它们的旋向相反,但是具有相同的螺旋直径、螺旋长度、螺旋缠绕程度和纤维直径。较大尺寸的催化剂粒子易生长直线型纳米碳纤维。     

阵列碳纳米管薄膜厚度调控研究

采用化学气相沉积法制备了阵列碳纳米管薄膜,对薄膜生长厚度进行了系统研究。利用扫描电子显微镜(SEM)、拉曼光谱(Raman)对样品形貌以及结构进行了表征。结果发现,在相同的生长时间和一定的催化剂浓度范围内,阵列碳纳米管的薄膜厚度随催化剂浓度提高而增加;在生长时间相同时,阵列碳纳米管薄膜厚度随载气流速的增加而降低,且下降趋势近似为线性;随着生长时间的增长,阵列碳纳米管薄膜的厚度也随之增加,且在前60min生长速度最快达到24μm/min,60min之后生长速度减缓。     

爆炸辅助气相沉积法制备炭纳米线的研究

根据爆炸辅助气相沉积法生长碳纳米管的机理,设计了两种制备炭纳米线的方案:(1)使用低活性铁-镍二元金属催化剂;(2)对钴催化剂作用下碳纳米管的生长实施冷冻。透射电子显微镜显示这两种方法制备的炭纳米线均为纳米颗粒组装而成,具有非常粗糙的表面。其中,使用铁-镍二元催化剂所制炭纳米线直径分布不均匀,黏结情况严重;而在冷冻钴催化剂作用下炭纳米管生长过程所得的炭纳米线直径分布比较均匀,黏结情况也大为减少。这两种纳米线的差别与金属催化剂的活性有关。光催化降解亚甲基蓝实验表明:冷冻碳纳米管生长所得炭纳米线具有良好的催化辅助功能,可以提高ZnS纳米晶的光催化活性。     

碳纳米团簇向碳纳米纤维相转变机理研究

为了能够快速且大面积生长碳纳米纤维,研究碳纳米纤维的形成、转变及在各种物理、化学环境下的反应机理,应用等离子化学气相沉积(PECVD)方法,以CH4为反应气体,FeCl2为催化剂在玻璃衬底上生长碳纳米薄膜.应用扫描电镜(SEM)观察了碳纳米纤维薄膜的表面形貌,拉曼(Raman)光谱分析了碳纳米纤维的结构组成.结果表明,无催化剂时薄膜主要由纳米团簇构成,而催化作用下薄膜呈纤维状生长,纳米纤维为典型的碳纳米管石墨特征峰.在温度,气压,催化剂等反应条件中,FeCl2催化剂对碳纳米薄膜的取向生长起决定性作用,通过调节催化剂的浓度与分布,可有效改变碳纳米纤维的密度与分布.     

炭纤维表面生长碳纳米管

采用化学气相沉积工艺在炭纤维表面生长了碳纳米管,并观察了它的微观形貌,且对其影响因素进行了初步研究.结果表明:纤维表面的纵向沟槽可以负载催化剂粒子,是生长碳纳米管的物理基础;催化剂的浓度太高,金属粒子容易团聚长大,所得碳纳米管的管径较大;而催化剂浓度太低,则不能在炭纤维整个表面均匀生长碳纳米管;最佳的催化剂溶液的浓度是0.05mol/L的硝酸钴.比较了铁、钴、镍三种过渡金属催化剂,从形成的碳纳米管的质量来看,钴催化剂最佳.     

The effect of temperature on the growth of carbon nanotubes on copper foil using a nickel thin film as catalyst

Growth of carbon nanotubes (CNTs) on bulk copper foil substrates has been achieved by sputtering a nickel thin film on Cu substrates followed by thermal chemical vapor deposition. The characteristics of the nanotubes are strongly dependent on the Ni film thickness and reaction temperature. Specifically, a correlation between the thin film nickel catalyst thickness and the CNT diameter was found. Two hydrocarbon sources investigated were methane and acetylene to determine the best conditions for growth of CNTs on copper. These results demonstrate the effectiveness of this simple method of directly integrating CNTs with highly conductive substrates for use in applications where a conductive CNT network is desirable.     

Influence of co-catalyst on growth of carbon nanotubes using alcohol catalytic CVD method

This paper describes the influence of a co-catalyst on growth of carbon nanotubes (CNTs) by alcohol catalytic chemical vapour deposition (ACCVD) method. Silicon wafers covered with thermal oxide or polycrystalline diamond thin film were used as substrates. Ni thin film supported with Al, Cu or Ti was used as a catalyst. The films were deposited by pulsed laser deposition technique. Comparison of the various types of the co-catalyst (Al, Cu, Ti) leads to the conclusion that Cu co-catalyst is suitable for producing very thin single wall carbon nanotubes (SWCNTs) and combination of Al and Ni provide a good condition to the catalytic growth of CNTs. In addition, we observed also the influence of the various diffusion barriers (thermal oxide and polycrystalline diamond) on growth of CNTs. Prepared samples were analysed by Raman spectroscopy (RS) and scanning electron microscopy (SEM).     

Synthesis of carbon nanotubes using Ni95Ti5 nanocrystalline film as a catalyst

Carbon nanotubes (CNTs) were synthesized by low-pressure chemical vapour deposition (LPCVD) using N2:C2H2:H2 gas mixtures on nanocrystalline Ni95Ti5 film. This nanocrystalline film was deposited on silicon substrate using vapour condensation method. The growth temperature and growth time was kept at 800 degrees C and 30 mins, respectively and the pressure was maintained at 10 Torr. The growth mechanism of CNTs was investigated using FESEM, TEM, HRTEM, and Raman Spectroscopy. From FESEM image of Ni95Ti5 nanocrystalline film, it is clear that the particle size varies from 5-10 nm. EDX analysis suggests that Ni95Ti5 alloy contains Ni and Ti both. It is clear from TEM images that CNTs are multiwalled with the diameter varying from 10-30 nm and length of several micrometers. HRTEM image shows that the structure of these multi-walled nanotube (MWNTs) is bamboo-shaped and the catalyst exists at the tip of MWNTs. Fourier Transform Raman Spectroscopy confirmed that graphitic structure of as-prepared CNTs. Field emission measurements reveal that the carbon nanotubes grown for 30 mins showed a turn-on field of 7.2 V/microm, when the current density achieves 10 microA/cm2. The field enhancement factor was calculated to be 708.50 for carbon nanotubes grown for 30 mins.     

Effect of catalyst thickness and plasma pretreatment on the growth of carbon nanotubes and their field emission properties

We demonstrated that the diameter and the density of carbon nanotubes (CNTs) which had a close relation to electric-field-screening effect could be easily changed by the control of catalytic Ni thickness combined with NH3 plasma pretreatment. Since the diameter and the density of CNTs had a tremendous impact on the field-emission characteristics, optimized thickness of catalyst and application of plasma pretreatment greatly improved the emission efficiency of CNTs. In the field emission test using diode-type configuration, well-dispersed thinner CNTs exhibited lower turn-on voltage and higher field enhancement factor than the densely-packed CNTs. A CNT film grown using a plasma-pretreated 25 angstroms-thick Ni catalyst showed excellent field emission characteristics with a very low turn-on field of 1.1 V/microm @ 10 microA/cm2 and a high emission current density of 1.9 mA/cm2 @ 4.0 V/microm, respectively.     

The influence of Ni catalyst on the growth of carbon nanotubes on Si substrates

This article treats the influence of the treatment of a Ni catalyst upon the growth of carbon nanotubes in alcohol catalytic chemical vapour deposition (AC CVD) equipment. Prior to the growth of diamond, a thin film of Ni was deposited on a silicon substrate by magnetron sputtering. We observed that a combination of annealing of the Ni catalyst in vacuum and NH₃ had a positive effect upon the growth of carbon nanotubes (CNTs). The prepared CNTs were analysed by scanning electron microscopy and Raman spectroscopy.     

镁-镍合金催化剂制备及纳米碳管生长模式研究

采用多元醇法制备镁-镍合金纳米粉末,并以此为催化剂制备纳米碳管,利用比表面和孔径分布测定仪、X射线衍射仪和透射电镜,研究镁-镍合金催化剂的性能和纳米碳管的生长模式。结果表明:Mg∶Ni值对镁-镍合金催化剂特性影响较大,其中Mg∶Ni为1的催化剂颗粒比表面积较大且平均粒径较小;聚乙烯吡咯烷酮(PVP)用量增大,有利于提高催化剂颗粒的比表面积、减小平均粒径,但用量过大不利于Mg2Ni合成。在以镁-镍合金为催化剂制备碳纳米管的过程中,首先在催化剂表面形成碳膜,随后形成的碳膜将前期形成的碳膜及催化剂颗粒向外推挤,催化剂颗粒移动后遗留下中空隧道,最终形成碳管,由于纳米碳管尖端的催化剂颗粒反应后失去催化活性,碳管的生长动力主要来自碳管根部。     

The evolution of carbon nanotubes during their growth by plasma enhanced chemical vapor deposition

During the growth of carbon nanotubes (CNTs) by plasma enhanced chemical vapor deposition (PECVD), plasma etching is the crucial factor that determines the growth mode and alignment of the CNTs. Focusing on a thin catalyst coating (Ni = 5 nm), this study finds that the CNT growth by PECVD goes through three stages from randomly entangled (I-CNTs) to partially aligned (II-CNTs) to fully aligned (III-CNTs). The I-CNTs and II-CNTs are mostly etched away by the plasma as time goes by ending up with III-CNTs as the only product when growth time is long enough. However, with a thickness of the catalyst coating of 10 nm or more, neither I-CNTs nor II-CNTs are produced, but III-CNTs are the only type of CNTs grown during the whole growth process. During the growth of III-CNTs, the catalyst particles (Ni) stay on the tips of each of the aligned CNTs and act as a 'safety helmet' to protect the CNTs from plasma ion bombardment. On the other hand, it is also the plasma that limits the growth of III-CNTs, since the plasma eventually etches all the catalytic particles out and stops the growth.     

Effect of Co and Ni nanoparticles formation on carbon nanotubes growth via PECVD

The effect of cobalt (Co) and nickel (Ni) nanoparticle catalysts on the growth of carbon nanotubes (CNTs) were studied, where the CNTs were vertically grown by plasma enhanced chemical vapour deposition (PECVD) method. The growth conditions were fixed at a temperature of 700 °C with a pressure of 1000 mTorr for 40 minutes with various thicknesses of sputtered metal catalysts. Only multi-walled carbon nanotubes are present from the growth as large average diameter of outer tube (～10–30 nm) were measured for both of the catalysts used. Experimental results show that high density of CNTs was observed especially towards thicker catalysts layers where larger and thicker nanotubes were formed. The nucleation of the catalyst with various thicknesses was also studied as the absorption of the carbon feedstock is dependent on the initial size of the catalyst island. The average diameter of particle size increases from 4 to 10 nm for Co and Ni catalysts. A linear relationship is shown between the nanoparticle size and the diameter of tubes with catalyst thicknesses for both catalysts. The average growth rate of Co catalyst is about 1.5 times higher than Ni catalyst, which indicates that Co catalyst has a better role in growing CNTs with thinner catalyst layer. It is found that Co yields higher growth rate, bigger diameter of nanotube and thicker wall as compared to Ni catalyst. However, variation in Co and Ni catalysts thicknesses did not influence the quality of CNTs grown, as only minor variation in I_G/I_D ratio from Raman spectra analysis. The study reveals that the catalysts thickness strongly affects not only nanotube diameter and growth rate but also morphology of the nanoparticles formed during the process without influencing the quality of CNTs.     

施镀时间和浓度对碳纳米管镀Ni层厚度的影响

为降低碳纳米管的表面活化能, 改善碳纳米管与金属基体的相容性, 采用化学镀的方法, 在碳纳米管表面镀覆一层金属Ni。研究了施镀时间和镀液浓度对碳纳米管表面镀Ni层厚度的影响。结果表明: 随着施镀时间延长, Ni沉积颗粒变大导致镀Ni层变厚; 镀液浓度增加, 碳纳米管表面沉积的Ni颗粒增多, 镀Ni层逐渐致密。本实验工艺条件下, 镀液浓度为0.08 mol/L, 反应时间为30 min时, 可以在碳纳米管表面镀覆一层界面结合良好且致密的Ni层, 其厚度约为10 nm。热处理能有效缓解镀Ni层应力, 改善界面结合。     

Force output, control of film structure, and microscale shape transfer by carbon nanotube growth under mechanical pressure

We demonstrate that a film of vertically aligned multiwall carbon nanotubes (CNTs) can exert mechanical energy as it grows, and in our experiments the average force output is approximately 0.16 nN per CNT, for CNTs having an outer diameter of 9 nm and five walls. The film thickness after a fixed growth time and the alignment of CNTs within the film decrease concomitantly with increasing pressure which is applied by placing a weight on the catalyst substrate prior to growth, and CNTs grown under applied pressure exhibit significant structural faults. The measured mechanical energy density of CNT growth is significantly less than the energies of primary steps in the CNT formation process yet, based on the film volume, is comparable to the energy density of muscle and based on the volume of CNTs is comparable to hydraulic actuators. We utilize this principle to fabricate three-dimensional structures of CNTs which conform to the shape of a microfabricated template. This technique is a catalytic analogue to micromolding of polymer and metal microstructures; it enables growth of nanostructures in arbitrarily shaped forms having sloped surfaces and nonorthogonal corners and does not require patterning of the catalyst before growth.